Treatment of protein-containing textile materials and products thereof



Patentecl Aug. 21, 1951 TREATMENT OF PROTEIN-CONTAININ G TEXTILE MATERIALS AND PRODUCTS THEREOF Arthur S. Nyquist, Cos Cob, Conn., assignor to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application May 17, 1947,

Serial No. 748,846

17 Claims (Cl. 117141) This invention relates to the treatment of protein-containing textile materials and to the products thereof. More particularly, the invention is concerned with a process of treating protein-containing textile materials, for example wool and wool-containing fabric and other textile materials, to impart improved properties thereto by treating, more particularly impregnating or coating and impregnating, the textile material with a composition comprising a reactive product of polymerization (that is, a polymerization product which is capable of further reaction, e. g., to an insoluble polymer of higher molecular weight) of a polymerizable composition includingby weight, (a) from about 10% to 100% of a compound represented by the general formula where R represents a hydrocarbon radical selected from the class consisting of alkyl, aralkyl, aryl and alkaryl radicals containing not more than 8 carbon atoms, e. g., methoxyethyl acrylate, benzoxyethyl acrylate, phenoxyethyl acrylate, methylphenoxyethyl acrylate, etc., and (b) from about 90% to (that is to say, up to about 90%) of a lower alkyl ester of acrylic acid, e. g., ethyl acrylate. The resulting textile material is heated at a temperature, e. g., at a temperature within the range of from about 200 F. to about 300 F., and for a period of time sufficient to cure the said polymerization product substantially completely. The cured polymerization product is substantially water-insoluble. The scope of the invention also includes the products obtained by treating the textile material.

Protein-containing textile materials, for instance wool-containing textile materials such as loose wool itself and yarns, threads and woven, felted and knitted cloth composed of or containing wool have a very undesirable tendency to felt and shrink when subjected to ordinary washing operations. The tendency of these protein-containing textile materials to felt and shrink is generally due to curling and intertwining of the protein fibers as the fabrics are wetted and subjected to the mechanical movements of the washing process. As a result, the textile material becomes more closely compacted, thicker and has a considerably reduced area.

A number of different methods have been proposed for the treatment of textile materials formed of or containing wool or other protein fibers in order to prevent or decrease felting and shrinking. In many cases such reduction in felt- 2 ing and shrinking tendencies has been obtained at the sacrifice of some other desirable property of the material. Some treatments damage the fiber and reduce the wearing qualities while others impart an undesirable harshness to the fabric. Other treatments are not permanently effective and may even cause an ultimate increase in shrinkage. Still other shrink-proofing methods are difficult to apply with uniformity and create hazardsto the workers involved in their applications.

The present invention is based on my discovery that protein-containing textile materials, e. g., wool and wool-containing textile materials, when treated with a reactive polymerization product of the kind described in the first paragraph of this specification yield a treated material which has excellent shrinkage resistance, increased tensile strength, a soft feeling to the touch and a permanent and improved finish which remains after laundering. For example, when a toluene solution containing (1) a soluble, reactive copolymer of, by weight, '75 parts of ethyl acrylate and 25 parts of ethoxyethyl acrylate and (2) a catalyst for accelerating the curing of (1) was applied to a piece of woolen goods and the treated goods was heated to evaporate the solvent and to cure the copolymer substantially completely, the treated woolen material had a soft hand, a substantially permanent finish and even after five launderings (10 minutes each in a soap solution followed by drying) showed a shrinkage of only 5.3% and, after further washing for 1 hour followed by drying, a shrinkage of only 6.4%. In marked contrast the same kind of wool in untreated state showed a shrinkage of 45% after five washing cycles of 10 minutes each followed by minutes washing. In some cases an even greater improvement in the resistance of the treated wool to shrinkage has been obtained depending, for instance, upon the particular wool treated, the particular polymer or copolymer employed and the particular treating technique. Thus, I have secured treated wools which showed as low as 1.9% shrinkage after five washing cycles of 10 minutes followed by drying and a shrinkage of only 2.2% after washing for an additional hour. Furthermore, treated textile materials obtained by practicing my invention have considerably enhanced tensile strength as compared with the untreated textile. It was quite unexpected and unpredictable that reactive polymers and copolymers of the kind used in practicing the present invention would impart such improved shrinkage resistance and tensile strength to a protein-containing textile material, specifically a woolen fabric. It also was quite surprising and unobvious that this shrinkage resistance was imparted to the woolen goods without materially lessening its softness to the touch.

By employing the textile-treating agents of the kind with which this invention is concerned, it is possible to obtain equally as good or better control of the shrinkage of, for example, wool than is possible by the use of conventional treating agents. Another advantage accruing from my invention is that protein-containing textile materials, more particularly wool-containing textile materials, which have been treated with a composition comprising a reactive polymer or copolymer of the kind described in the first paragraph of this specification usually reach rather quickly a point of maximum or substantially maximum shrinkage upon repeated launderings, whereas the same textiles when untreated or when treated with some of the prior treating agents often show increasingly higher percentage increases in shrinkage upon further launderlng.

This also was quite surprising and unexpected and in no way could have been predicted.

Another advantage flowing from my invention is that, if desired, a somewhat lesser amount of treating agent may be employed than is customarily required in the treatment of a protein-containing textile with most conventional textiletreating agents in order to render it resistant to shrinkage and creasing. For instance, in the case of wool as much as about 16%, by weight of the wool, of a conventional treating agent may be required in order to obtain satisfactory shrinkage and crease control of the'woolen fabric, whereas with the reactivepolymerization products used in practicing the present invention satisfactory results usually are obtained with, by weight, about 8 or 10 or less of the reactive polymerization product, based on the weightof the dry, untreated wool. The use of higher amounts, however, for example as much as or by weight of the dry, untreated material, or even higher (e. g., or of the polymerization product is not precluded and in some cases even may be desirable, for instance when it is desired to produce a weighted protein-containing fabric.

In practicing my invention I treat a proteincontaining textile material, e. g., wool, with a composition comprising a reactive product of polymerization of a polymerizable composition including (a) from about 10% to 100% of a compound represented by the formula Where R represents a hydrocarbon radical selected from the class consisting of alkyl, aralkyl, aryl and alkaryl radicals containing not more than 8 carbon atoms and (b) from about 90% to 0% of a lower alkyl ester of acrylic acid. Illustrative examples of radicals which R in the above formula, which is the same as Formula I, may represent are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert.-butyl, amyl, isoamyl, n-octyl, Z-ethylhexyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, benzyl, phenylethyl, phenyl, tolyl, xylyl, ethylphenyl and isomeric forms of such radicals. Compounds embraced by the above formula are acrylic esters of a mono ether of ethylene glycol and may be prepared, for example, by direct esterification of acrylic acid with the ethylene glycol mono ether or by eifecting an alcoholysis' reaction between methyl or ethyl acrylate and the glycol mono ether. Such reactions are effected in the presence of a suitable inhibitor of polymerization. The monomeric ester may be polymerized to yield a reactive polymer as described more fully hereafter.

Instead of effecting a complete interesterification between a lower alkyl ester of acrylic acid, e. g., methyl acrylate, ethyl acrylate, etc., and an ethylene glycol mono ether, a partial ester exchange may be effected. For example, the reaction may be allowed to proceed until, for example, from 10 to of the alkyl acrylate has been transesterified, yielding a mixture of alkyl acrylate and oxyethyl acrylate. The resulting product may then be polymerized and used in treating protein-containing textile materials in the same manner as the reactive polymers and copolymers hereinbefore described.

The reactive copolymers are produced by mixing a compound of the kind embraced by the above formula, or a mixture of such compounds, with a lower alkyl ester of acrylic acid, e. g., methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec.-butyl acrylate, tert.butyl acrylate, amyl acrylate, etc., or a mixture of such acrylates, in the percentage proportions hereinbefore given. The mixed ingredients are then copolymerized.

The monomeric ester or mixture of monomeric esters may be polymerized or copolymerized in any suitable manner. For example, I may use heat, light or heat and light, with or Without a polymerization catalyst, e. g., benzoyl peroxide or other organic or inorganic peroxide, in effecting the polymerization or copolymerization reaction. Ultraviolet light is more effective than ordinary light. Preferably a catalyst is employed for accelerating the polymerization or copolymerization of the simple or mixed esters. If desired, the polymerizable composition may be polymerized in emulsion or in solution state. In the latter case, various inert organic solvents may be employed, e. g., toluene, xylene, dioxane, ethers (e. g., dibutyl ether), esters (e. g., butyl acetate), chlorobenzene, ethylene dichloride, ketones (e. g., methyl ethyl ketone), alcohols (e. g., ethanol, butanol, etc), as well as others. The temperature of polymerization or copolymerization may be varied as desired or as conditions may require, but ordinarily will be within the range of from about 20 C. to about C. when the reaction is effected in the absence of a solvent. When the reaction is effected in solution state, then a temperature at or approaching the boiling temperature of the solution generally is used. In all cases the temperature of polymerization 01' copolymerization is below the decomposition temperature of the monomeric material or materials.

In polymerizing the monomer or mixture of monomers, I prefer to use heat and a catalyst for accelerating the polymerization. Illustrative examples of catalysts that may be employed are inorganic peroxides, e. g., barium peroxide, magesium peroxide, zinc peroxide, etc. Such peroxides are particularly useful when used in conjunction with promoters or other catalysts such, for instance, as an anhydride of an organic acid, e. g., phthalic anhydride, succinic anhydride, etc. Hydrogen peroxide also is a suitable catalyst for the polymerization reaction. Illustrative examples of organic peroxides that may be used are the dialkyl peroxides, e. g., diethyl peroxide, dipropyl peroxide, dilauryl peroxide, dioleyl peroxide, di-

'stearyl peroxide, di-(tert.-butyl) peroxide and di- (tert.-amyl) peroxide, such peroxides often being designated as ethyl, propyl, lauryl, oleyl, stearyl, tert-butyl and tert.-amyl peroxides; the alkyl hydrogen peroxides, e. g., tert.-butyl hydrogen peroxide (tert.-butyl hydroperoxide), tert.-amyl hydrogen peroxide (tert.--amyl hydroperoxide), etc.; symmetrical diacyl peroxides, for instance peroxides which commonly are known under such names as acetyl peroxide, pro-pionyl peroxide, lauroyl peroxide, stearoyl peroxide, malonyl peroxide, succinyl peroxide, phthaloyl peroxide, benzoyl peroxide, etc.; fatty oil acid peroxides, e. g., coconut oil acid peroxides, etc.; unsymmetrical or mixed diacyl peroxides, e. g., acetyl benzoyl per-oxide, propionyl benzoyl peroxide, etc.; terpene oxides, e. g., ascaridole, etc.; salts of inorganic per-acids, e. g., ammonium persulfate, sodium persulfate, potassium persulfate, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, sodium per-phosphate, potassium perphosphate, etc.; metal salts of organic acids, e. g., cobalt and manganese resinates, linoleates, naphthenates, etc.; oxygen; etc. A plurality of catalysts such as above mentioned may be employed if desired, e. g., a cornbination of benzoyl peroxide or other peroxide and cobalt naphthenate or other metal salt of an organic acid.

Any suitable amount of catalyst may be used, but in general the catalyst concentration will be within the range of about 0.005 to 6%, more particularly within the range of 0.05 to 5%, by weight of the monomer or mixture of monomers.

The reactive polymeric or copolymeric composition may be applied to the protein-containing textile material in any suitable manner. The textile material may be contacted with the polymer or copolymer in undiluted state, or the polymer or copolymer may be applied in the form of a solution or dispersion thereof. In all cases the amount of treating agent which is deposited or incorporated in the protein-containing textile material, e. g., wool or a wool-containing textile material, is at least about 2% by weight, based on the dry weight of the textile material. The amount will vary depending, for instance, upon the particular protein-containing textile material that is undergoing treatment, the particular polymer or copolymer employed, the kind of emulsifying agent used if applied from a dispersion, whether or not a weighted textile is desired, etc. Ordinarily, however, the amount of polymer or copolymer that is incorporated in the textile material is from about 3 to about by weight of the dry, untreated material, but if a weighted textile is wanted it may be much more, for example as much as about 30% or more by Weight of the dry, untreated textile.

In general, better results are obtained if an additional amount of catalyst is incorporated into the textile-treating composition, e. g., a solution or aqueous dispersion or an aqueous-organic solvent dispersion of the polymer or copolymer, prior to treating the textile material. Such catalysts may be the same or different from those used in preparing the reactive polymer or copolymer (partial polymer or copolymer) and the amount of catalyst employed may be of the same order, e. g., from 0.005 to 6%, more particularly from 0.05 to 5%, by weight of the polymer or copolymer, as was used in the initial polymerization operation. In some cases better results are obtained by allowing the treating composition to age at a suitable temperature, e. g., at room temperature (-30 C.), for a period ranging from ing it to the textile material.

If the textile material to be treated contains fats, oils, or other contaminants, it is first thoroughly cleaned in any suitable manner prior to treatment with the polymer or copolymer. Various methods may be employed in applying the acrylate composition. For example, the dry textile material may be immersed in the liquid composition and then passed through suitable rolls, as in a padder or mangle, to insure uniform impregnation and to remove excess treating agent. However, the textile material may be impregnated or coated and impregnated by other methods, for example, by spraying or brushing a solution or dispersion of the polymer or copolymer upon the textile or by applying thereto a liquid polymer or copolymer in undiluted state. Or, the solid, thermoplastic acrylate polymer or copolymer itself may be combined with the textile material as by passing a sheet or cloth of the same, having thereon or therein the said polymer or copolymer in finely devided state, between hot rolls. The impregnating operation and the concentration of the polymer or copolymer (in solution, dispersion or other state) are adjusted so that the amount of polymer or copolymer which is taken up by the textile material will be most effective and economical in producing the desired results.

If the reactive polymer or copolymer has been applied in dissolved or dispersed state to the textile material, the treated textile is heated to volatilize the inert, volatile organic liquid (if the polymer or copolymer was applied as a solution thereof), or to volatilize the water (if the polymer or copolymer was applied as an aqueous dispersion thereof), or to volatilize the water and the inert organic liquid (if the polymer or copolymer was applied in the form of an inert organic liquidwater dispersion) and, also, to convert in situ the reactive polymer or copolymer to a substantially completely cured condition, in which form it is substantially water-insoluble. The cured polymers and copolymers, which are formed in situ, also are insoluble or substantially insoluble in conventional organic solvents, e. g., toluene, xylene, alcohols (ethanol, etc.), carbon tetrachloride, ethers (e. g., diethyl ether, etc.) and others.

Any suitable elevated temperature may be employed, but in no case should the temperature be so high as to char or otherwise detrimentally affect the textile material. For instance, with most protein-containing textiles temperatures within the range of from about 200 F. to about 300 F. may be used satisfactorily. Ordinarily, temperatures at or slightly above the boiling pointof water or of the particular inert organic liquid solvent employed (if any) are sufiicient to effect the desired result. Of course, it will be understood by those skilled in the art that there is a time-temperature relationship involved: the lower the temperature the longer the time of heating, and the higher the temperature the shorter the heating period. The temperature also will vary somewhat with, for instance, the particular protein-containing textile which has been treated and the particular polymer or copolymer employed.

In some cases it may be desirable to give the impregnated textile material an after-treatment such, for instance, as one or another of those shown in some of the examples which follow, e. g., a treatment with a dilute, aqueous, acidified solution of formaldehyde. When such aftertreatments are to be applied, the wet impregnated wool maybe dried at a lower temperature (e. g-.;

at about 130-190 F.) immediately followingthetreatment with the acrylate composition or, if desired, at the same temperatures (e. g., 200 to 300 F.) which ordinarilyv are used to dry the impregnated textile material and to cure the acrylate composition in situ to a substantially waterinsoluble condition. After treatment with a formaldehyde solution or other liquid after-treating agent, the treated textile is heated at a suitable temperature (e. g., at from about 200 F. to about 300 F.) and for a time sufficient to develop the optimum shrinkage-resistance and other improved properties in the textile.

After the textile material, e. g., woolen fabric material, has been treated as hereinbefore described, it may be given, if desired or necessary, a mild soaping for a short period before finishing. The textile material then may be given the usual finishing treatments required in a particularcase, e. g., decatizing, brushing, shearing, pressing, etc.

In order that those skilled in the art better may understand how the present invention may be carried into effect, the following examples are given by way of illustration and not by way of limitation. All parts are by weight.

Example 1 Parts Ethyl acrylate 75.0 Ethoxyethyl acrylate 25.0 Benzoyl peroxide 0.2 Toluene 60.0

The toluene was placed in a 3-necked reaction I vessel provided with a reflux condenser, a stirrer and a dropping funnel. The vessel was heated in an oil bath maintained at about 135 C., while passing a slow stream of carbon dioxide into the vessel. a homogeneous solution, which then was added slowly over a period of 35 minutes to the toluene. Copolymerization of the ethyl acrylate and ethoxyethyl acrylate proceeded satisfactorily without becomingv vigorous at anytime during the addition. Heating was continued for 45 min utes more. The resulting viscous copolymer solution was allowed to cool, after which it was diluted with additional toluene to yield a solution containing approximately 10% by weight of copolymer.

A piece of woolen goods was immersed in the 10% toluene solution of copolymer to which had been added 5% by weight of benzoyl peroxide based on the weight of the copolymer anda trace of cobalt naphthenate. (The benzoyl peroxide, in this and other examples which follow, was dissolved in a small amount of toluene, which then was added to the copolymer solution.) The treat-v ed wool was passed through squeeze rolls, after which it was framed, air-dried for a short period, and then heated for 9 minutes at 290 F. After cooling to room temperature, the sample was removed from the frame, allowed to remain undise turbed for about 16 hours and was then measured prior to laundering. The method of laundering was a modification of the standard method of the A. A. T. C. 0., and involved heating-for20to 30 minutesat 240 F. while drying after each washing. After a cycle of 5 washing minutes in soap solution) and drying operations, the dried,

treated cloth showed a shrinkage-of only 5.3%. After 5 cycles of 5 washing and drying operations and a washing of 1 hour in soap solution after each cycle, the dried, treatedcloth showed a The other ingredients were mixedto yield a 8 shrinkage of only 8.3 untreated woolen cloth (sample A) after five washing cycles of 10 minutes each followed by 60 minutes washing showed a shrinkage of The shrinkage data on the treated woolen sample are shown below:

Percent shrinkage After five washing cycles of 10 minutes each 5.3 After 60 minutes washing 6.4 After five washing cycles of 10 minutes each 7. After 60 minutes washing 7.2 After five washing cycles of 10 minutes each 7.8 After 60 minutes washing 7.8 After five washing cycles of '10 minutes each 8. After 60 minutes washing 8.6 After five washing cycles of 10 minutes each 3.0 After 60 minutes washing 8.3

The treated wool was full and soft.

Example 2 The same formula and essentially the same procedure were followed as described under Example l with the exception that the mixture of ethyl acrylate, ethoxyethyl acrylate and benzoyl peroxide was added to the mildly refluxing toluene over a period of 11 minutes. Also, after 39 minutes further heating, an additional 0.2 part of benzoyl peroxide dissolved in 5 parts of toluene was added to the reaction mass and heating was continued for 2 hours more. The cooled copolymer solution, which was fairly viscous, was diluted with additional toluene to yield a solution containing approximately 10% by weight of copolymer.

The 10% copolymer solution was used in treating, wool as described below:

Nos. 1 and 2.-Samples of two different kinds of woolen cloth were treated as described under Example 1 with the copolymer solution to which had been added 5% by weight of benzoyl peroxide based on the weight of the copolymer and a trace of cobalt naphthenate. The shrinkage data on the untreated wool (sample B) used in test No. 1 are shown below:

Per cent shrinkage After five washing cycles of 10 minutes each followed by 60 minutes washing 44.5 After five more washing cycles of 10 minutes each followed by 60 minutes washing 49.0

In test No. 2 the same kind of wool (sample A) was treated as was used in Example 1.

No. .3.The 10% copolymer solution was aged for 3 weeks at room temperature, after which 5% by weight of benzoyl peroxide based on the weight of the copolymer was added thereto, and the resulting solution was used in treating woolen cloth as described under Example 1.

No. 4.--Same as Nos. 1 and 2 with the exception that the unused portion of the copolymer solution employed in those tests was aged for 3 weeks before treating a piece of woolen cloth with the same.

No. 5.-The- 10% copolymer solution was aged for days and the aged solution, without adding more catalyst, then used in treating woolen cloth asset forth under Example 1.

No. 6.-S-ame as No. 3 with the exception that the unused portion of the copolymer solution employed in that test was aged for 113 days at room temperature, after which more benzoyl peroxide (about 1 to 3% by weight of the copolymer) was added to the solution. A piece of solution, and further processed as described In marked contrast,

After five washing under Example 1 including a heat treatment of the impregnated wool for 9 minutes at 290 F. The treated wool was immersed for a few minutes in an aqueous solution containing approximately 3.7% by weight of formaldehyde and which had been acidified to a pH of about 3 with acetic acid. The formaldehyde-treated wool was passed through squeeze rolls, after which it was framed, air-dried for a short period and then again heated for 9 minutes at 290 F.

No. 7 .Same as No. 6 with the exception that the unused portion of the copolymer solution was aged for 13 days at room temperature before treating woolen goods with the same, the time of heating at 290 F. was 18 minutes, and the after-treatment with acidified formaldehyde solution was omitted.

In tests Nos. 3 and 4 the same kind of wool (sample A) was treated as was used in test No. 2. In tests Nos. 5, 6 and '7 a different kind of wool (sample C) from that employed in tests Nos. 1 to 4, inclusive, was treated. The sample C wool showed a shrinkage of 27.8% after 2 cycles of 5 washing and drying operations and a washing of 1 hour in soap solution after each cycle.

The shrinkage data on the treated woolen samples are shown below:

Per Cent Shrinkage No.1 No.2 No.3 No.4 No.5 No.6 No.7

After five washing After five washing cycles of minuteseaeh 6.4 7.8105 8.0 9.2 3.1 5.6

After 60 minutes washing 6.9 7.8 8.6 8.9 3.9 5.3

cycles of 10 minutes each 7. 2 8.0 8. 6 7. 5 3. 9 6.1 After 60 minutes washing 6. 9 8. 6 8.3 9. 2 4. 4 6. 9

After five washing cycles of 10 minuteseach 7.2 8.3 8.6 9.2 6.4

utes each 6.9 7.8 9.2 10.0 6.4 After 60 minutes washing 9. 2 9. 7 6. 4

All of the treated woolen samples had a soft hand, that is, a soft feeling to the touch.

Example 3 Parts Ethyl acrylate 75 Ethoxyethyl acrylate 25 10% aqueous solution of a sodium salt of a sulfated long-chain alcohol 25 0.1% aqueous solution of potassium pe'rsulfate 25 Water 250 were heated together in a reaction vessel provided with a stirrer and a reflux condenser. After stirring vigorously for a few minutes to effect emulsification, the vessel was heated on a steam bath. After heating for about 8 minutes the refluxing became fairly vigorous and the rate of stirring was reduced. At the end of 12 minutes additional heating, refluxing had almost completely subsided. Heating was continued for an additional 40 minutes, after which unreacted monomers were removed by steam stripping for 15-20 minutes.

The resulting emulsion was diluted with water to form an emulsion containing approximately 10% by weight of copolymer. This emulsion was allowed to stand for 113 days and was then used, with and without further catalyst, in treating woolen goods as described under Example 1.

In one case (No. 1) the aged emulsion was used without adding any more catalyst. In another case (No. 2) a small amount (less than 1% by weight) of potassium persulfate, based on the amount of copolymer in the emulsion, was added to the aged emulsion before the latter was applied to the wool. While in a third case (No. 3), about 5% by weight of a 3% aqueous solution of hydrogen peroxide, also based on the amount of copolymer in the emulsion, was used as a catalyst in place of potassium persulfate before applying the aged emulsion to the wool. The same kind of wool (sample C) was treated in each case. The shrinkage data on the treated vool are shown below:

Per Cent Shrinkage No. 1N0. 2 No. 3

After five washing cycles of 10 minutes each. 8. 3 7. 5 6. 7 After 60 minutes washing 8. 9 8. 0 7. 5 After five washing cycles of 10 minutes each- 9. 2 8. 0 8. 0 After 60 minutes washing 9. 4 8. 3 7. 8 After five Washing cycles of 10 minutes each. 9. 2 8. 3 8. 3 After 60 minutes washing 9. 2 8. 3 4 7. 5 After five washing cycles of 10 minutes each. 8. 6 8.0 7. 8 After 60 minutes washing 8. 9 7. 8 7. 5 After five washing cycles of 10 minutes each 9.2 8. 6 7. 8 After 60 minutes washing 8.9 8.0 8.0

The treated wools were full and soft.

The unused portions of the emulsions to which the potassium persulfate and hydrogen peroxide had been added (Nos. 2 and 3, respectively) were allowed to stand for 84 days. To No. 2 was added more potassium persulfate (less than 1% by weight of the copolymer in the emulsion). The same kind of wool (sample C) as previously had been used was initially treated with each of these emulsions as described under Example 1. Thereafter each sample of wool, after heating for 6 minutes at 240 F., was immersed for a few minutes in an aqueous, approximately 25 C. solution containing about 3.7% by weight of formaldehyde and acidified to a pH of about 3.0 with acetic acid. The treated samples were then further processed and laundered as described under Example 4 The same formula and general procedure were followed as'deseribed under Example 1 with the exception that 25 parts of methoxyethyl acrylate was used in place of 25 parts of ethoxyethyl acrylate. The mixture of monomers and catalyst Was added to the toluene over a period of 26 minutes. Heating was continued for an additional 3 hours, after which the solution of the copolymer'was partly cooled and 100 parts of toluene added thereto while transferring the solution from the reaction vessel, yielding a solution containing approximately 35.8% of solids. lution was further diluted with toluene to yield a solution containing approximately by weight thereof of copolymer.

The 10% copolymer solution was used in treating woolen cloth (sample 'C) as described below:

No. 1.Benzoyl peroxide in an amount corresponding to about 1% by weight of the copolymer was added to thesolution before it was used in treating the wool, and the impregnated wool was further processed as described under Example 1.

No. 2. -Same as No. 1 with the exception that the solution was aged for 3 weeks at room temperature prior to use.

No. 3.-Same as No. 2 with the exception that the impregnated wool was heated for 18 minutes instead of 9 minutes at 290F.

N0. 4.Same as No. 2 with the exception that after treating the wool with the aged copolymer solution the impregnated wool was dried for about 30 minutes at 150 F., after which it was immersed for minutes in a dilute, aqueous,

' approximately C. solution of phosphoric acid having a pH of about 3.0, passed through squeeze rolls and then further processed as described under Example 1.

No.. 5.Same as No. 4 with the'exception that the phosphoric acid solution was heated to about N0. 6.Same as No. 4 with the exception that the dried wool was immersed for about 15 minutes in an aqueous, approximately 25 C. solution containing about 3.7% by weight of formaldehyde and acidified to a pH of about/3.0 with phosphoric acid.

No. 7 .-Same as No. 4 with the exception that the dried wool was immersed for about 15 min utes in water at about 25 C.

The shrinkage data on the laundered samples are shown below: a

Per Cent Shrinkage No.2 No.3 No.4 No.5 No.6 No.7

After five washing cycles of 10 minutes each After 60 minutes washing After five Washing cycles of 10 minutes each After 60 minutes washing After five washing cycles of 10 minutes each .l

After 60 minutes washing After five washing cycles of 10 minutes each All of the treated samples had a soft hand.

Example 5 then gradually subsided. Heating was continued This sofor'a total of '50 minutes, after which the reaction mass was steam stripped until free from the odorof monomers.

"The resulting emulsion was diluted with water to form an emulsion containing approximately 10% by weight of copolymer.

The "10% copolymer emulsion was used in treating woolen cloth (sample C) as described below:

No. 1.-Benzoy1 peroxide in an amount corresponding to about 1% by weight of the copolymer was added to the emulsion before it was used in treating the wool, and the impregnated :wool was further processed as described under Example 1.

N0. 2.Same as No. 1 with the exception that the emulsion was aged for3 Weeks at room. temperature prior to use.

No. 3.-Sarne as No. 2 with the exception that after treatingthe wool with the aged copolymer emulsion the impregnated wool was dried for about 30 minutes at -F., after which it was immersed for 15 minutes in an aqueous, approximately 25 C. solution containing about 3.7% by weight of formaldehyde and acidified to a pH of about 3.0 with acetic acid, passed through squeeze'rolls and then further processed as de scribed under Example .1.

N0.- 4.-Same-as No. 3 with the exception that the impregnated wool was heated for 9 minutes zit-290 -F. before immersing it in the acidified formaldehyde solution.

No. 5.Same as No. 3 with the exception that the dried, impregnated wool was immersed for v15 minutes in a dilute, aqueous, approximately 25 C. solution of acetic acid having a pH of about 3.0 instead of in an acidified formaldehyde solution.

The shrinkage data on the laundered samples are shown below:

Per Cent Shrinkage No. 1N0. 2 N0. 3 No. 4 No. 5

After five Washing cycles of 10 minutes each 5. 3 -4. 7 5. 3 5.0 5. 6 After 60 minutes washing 5. 3 5. 3 5.8 5. 3 6. 1 After five washing cycles of 10 minutes each 6.1 '6. l 6.1 5. 8 7. 2 After 60 minutes washing. .l. 5. 8 6. 7 7. 5 6. 7 7. 5 After five washing cycles 01' 10 m nutcs each 6.1 6.1 6. l 5. 8 6. 7 After 60 minutes Washing. 6.1 5. 8 5. 8 5. 5 6. After five washing cycles of 10 minutes each 659 After 60 minutes washing 6.9

:All of the treated samples had a soft hand.

Eatarnple 6 Parts Ethoxyethyl acrylate 26.0 Ethyl acrylate 78.0 Benzoyl peroxide 0.42 Toluene W 50.0

sified by adding it slowly to 750 parts of water containing 0.63% by weight thereof of an emulsifying agent, more particularly a sodium salt of a sulfated long chain alcohol, while agitating the latter with a Homorod unit. Agitation was continued more vigorously for minutes after adding the toluene solution of the copolymer, yielding a stable emulsion.

Two pieces of woolen goods (sample 'C) were immersed in the 10% copolymer emulsion to which had been added 5% by weight of benzoyl peroxide based on the weight of the copolymer. The same procedure was followed in treating the wool as described. under Example 1 with the exception that in one case (No. 1) the impregnated wool was heated for 9 minutes at 290 F., while in the other case (No. 2) the impregnated wool was heated for minutes at 240 F. The shrinkage data on the laundered samples are shown below:

Both of the treated samples had a soft hand.

Example 7 Parts Methoxyethyl acrylate 100.0 Benzoyl peroxide 0.4 Toluene 67.0

The above-stated amount of benzoyl peroxide was dissolved in the methoxyethyl acrylate. The resulting solution was added dropwise over a period of 28 minutes to 6'7 parts toluene heated under reflux conditions (bath temperature of about 135 C.) while slowly stirring the mass. Heating was continued for an additional .3 hours at the same bath temperature. After cooling the resulting toluene solution of the polymer, 100 parts of toluene was added thereto while transferring it from the reaction vessel, yielding a clear, moderately viscous solution containing about by weight of polymer. This solution was diluted with additional toluene to obtain a liquid composition containing about 10% by weight of polymer.

The polymeric solution was used in treatin woolen cloth (sample C) as described below:

No. 1.The same procedure was followed as described under Example 1 with the exception that 3% by weight of benzoyl peroxide, based on the weight of the polymer, was added to the solution prior to immersing the wool therein.

N0. 2.Same as No. 1 with the exception that the impregnated wool was dried for about 30 minutes at 150 F., after which it was immersed for 10 minutes in an aqueous, approximately 25 C. solution containing about 3.7% by weight of formaldehyde and acidified to a pH of about 3.0 with acetic acid, passed through squeeze rolls and then further processed as described under Example 1.

N0. 3.-The same procedure was followed as set forth under Example 1 with the exception that no additional catalyst was added to the polymeric solution prior to immersing the wool therein. The impregnated sample was dried, given an after- 14 treatment with an acidified formaldehyde solution and further processed as in test No. 2.

The shrinkage data on the laundered samples are shown below:

in the art that my invention is not limited to the specific treating agents named in the above illustrative examples nor to the particular methods of application therein described. Thus, instead of a reactive polymer of methoxyethyl acrylate (Example 7) I may use a reactive polymer of any other compound of the kind embraced by Formula I, e. g., a reactive polymer of ethoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, pentoxyethyl acrylate, hexoxyethyl acrylate, heptoxyethyl acrylate, octoxyethyl acrylate, cyclohexoxyethyl acrylate, benzoxyethyl acrylate, phenylethoxyethyl acrylate, phenoxyethyl acrylate, me'thylphenoxyethyl acrylate, etc.,- in treating a protein-containing textile material to improve its resistance to shrinking, its finish and other properties. Preferably I use a reactive copolymer of such oxyethyl acryla'tes with a lower alkyl ester of acrylic acid, e. g., methyl acrylate, ethyl acrylate and other lower alkyl acrylates of which numerous examples previously have been given. In making such copolymers, the proportions of monomers may be widely varied within the range of from about 10% to about 99.5% of the oxyethyl acrylate to from about 90% to about 0.5 of the lower alkyl acrylate, more particularly from about 15% to about of the oxyethyl acrylate, e. g., methoxyethyl acrylate, to from about 85% to about 15% of the lower alkyl acrylate, e. g., ethyl acrylate. Thus, I advantageously may use in treating woolen or other proteincontaining textile material a reactive copolymer which is the product of polymerization of a mixture containing, by weight, from about 15% to about 35 or 40% or more of an oxyethyl acrylate of the kind embraced by Formula I, e. g., methoxyethyl acrylate, ethoxyethyl acrylate, etc., and from about 85% to about 65 or 60% or less of a lower alkyl acrylate, e. g., methyl acrylate, ethyl acrylate, etc. The impregnated fabric or other textile material is then advantageously heated at a temperature within the range of from about 200 F. to about 300 F. for a period sufficient to cure in situ the said reactive polymerization product substantially completely.

Likewise, it will be understood that my invention is not limited to the use of toluene as a solvent either in the preparation of the polymeric or copolymeric material or in its application to a protein-containing textile material. 'Illustrative examples of other inert, volatile, organic liquids (that is, volatile, organic liquids which are non-reactive with the monomeric or partially polymerized materials), which may be used in the preparation ofv the treating agent or in applying it to the textile material in solution state or in the form of an organic liquid-water disper sion are: benzene, toulene, xylene, dioxane, ethers (e. g., diisopropyl ether, dibutyl ether, etc.), esters (e. g., butyl acetate, etc.), chlorinated hydrocarbons, for-instance-carbon tetrachloride, trichloroethylene, ethylene dichloride, chlorobenzenes (e. g., 1,3-dichlorobenzene, etc.), alcohols (e. g., ethanol, butanol, etc.), and other. If applied in the form of an organic liquid-water dispersion, the organic liquid is one which is immiscible with the water.

If the reactive polymer or copolymer is to be applied to the textile material in the form of a dispersion, specifically a Water dispersion or an organic liquid-water dispersion, any suitable emulsifying agent may be employed, e. g., the sodium salts of the sulfates of a mixture of lauryl and myristyl alcohols, dioctyl sodium sulfosuc- .cinate, sodium salts of alkylaromatic sulfonic acids (e. g., the sodium salt of isopropylnaphthalene sulfonic acid), quaternary ammonium salts (e. g., cetyl dimethyl ammonium chloride),

- etc.

The amount of polymer or copolymer in the solution or dispersion which is applied to the textile material may be varied considerably, but generally is Within the range of, by weight, from about to about 20 or 25% of the solution or dispersion. Good results have been obtained when the polymer or copolymer constituteda-bout by weight of the solution or dispersion. When solutions or dispersions containing about 10% by weight of polymer or copolymer are em- ,ployed, the amount of polymer or copolymer which is taken up by the textile material undergoing treatment is usually of the order of 8 to 10% by Weight of the dry untreated textile.

My process may be applied in the treatment of Various types of protein-containing textiles, for instance those formed of or containing Wool, silk, mohair, fur, leather, regenerated fibers or fabrics, e. g., those produced from casein, peanut, corn (zein) ,e g albumin, feathers (keratin), collagen, etc.; mixtures of such protein-containing textiles; and mixtures of such protein-containing textiles with other types of textiles, for instance those formed of cellulose or regenerated cellulose, e. g., cotton, linen, hemp, jute, ramie, sisal, cellulose acetate rayons, cellulose acetate-butyrate rayons, sapom'fied acetate rayons, cuprammonium rayons, ethyl cellulose, etc. My process also may be applied in the treatment of colored textile material as well as whites.

The reason why the reactive polymers of oxyethyl acrylates used in practicing my invention and copolymers thereof with a lower alkyl acrylate have the particular and peculiar property of imparting such outstanding shrinkage resistance :to a protein-containing textile material, specifically wool, is not now known to me, but it may depend upon or be influenced by the curing which takes place on the surfaces of the fibers of the textile. The reactive polymers and copolymers themselves, when exposed to air or when treated with a peroxide, undergo reaction leading to cross-linking or conversion to a substantially in- :soluble state. This effect of air or a peroxide seems to proceed when the polymer or copolymer is applied to a protein-containing textile material, specificallya woolen textile material, so that 'insolubilization or curing of the polymer or 00- 'ing the present invention may be used to supplement or in combination with conventional textile-treating compositions in the treatment of textiles to impart improved properties thereto.

In a manner similar to that hereinbefore described with particular reference to the treatment of protein-containing textile materials, e. g., wool, with reactive polymers of oxyethyl acrylates of the kind embraced by Formula I and with reactive copolymers of such oxyethyl acrylates with a lower alkyl ester of acrylic acid, other oxyethyl acrylates, e. g., the acrylic esters of the mono ethers of diethylene glycol or other acrylates possessing an oxygen bridge, may be employed. Alkacrylates possessing an oxygen bridge, e. g., oxyethyl methacrylates, oxyethyl ethacrylates, etc., also may be polymerized alone or with a lower alkyl ester of acrylic acid to yield a reactive polymer or copolymer which then may be used as a textile-treating agent. Instead of using a lower alkyl ester of acrylic acid in forming a copolymer of the same with an oxyethyl acrylate or alkacrylate, other compounds containing a CH2=C grouping may be used, more particularly compounds represented by the general formula R CHz=C where R represents a radical such, for example, as halogen (e. g., chlorine, bromine, etc.), aryl (e. g., phenyl, etc.), halogenoaryl (e. g., chlorophenyl, dichlorophenyl. etc.), alkaryl (e. g., tolyl, Xylyl, etc.), carbamyl, cyano and acyloxy (e. g., acetoxy, etc.), specifically styrene, the various chloro (e. g., monoand dichloro) and other halogeno styrenes, the various methyl styrenes (e. g., monoand dimethyl styrenes), acrylamide, acrylonitrile, vinyl acetate, etc. Such copolymers then may be used in treating textiles as hereinbefore described.

The terms textile and textile material as used generally herein and in the appended claims include within their meanings filaments, fibers, threads, yarns, twisted yarns, etc., as such or in woven, felted or otherwise formed fabrics, sheets, cloths and the like.

I claim:

1. A process of treating protein-containing textile material to improve the properties thereof which comprises treating said textile material with a reactive, partly polymerized product of polymerization of a polymerizable composition including, by Weight, from about 10% to 100% of a compound represented by the general formula where R represents a hydrocarbon radical selected from the class consisting of alkyl, aralkyl, aryl and alkaryl radicals containing not more than 8 carbon atoms and up to about of a lower alkyl ester of acrylic acid, the amount of the said polymerization product which is incorporated in the said textile material being from about 2% to about 30% by weight of the dry untreated textile, and heating the resulting treated material to cure the said polymerization product.

2. A process as in claim 1 wherein the lower alkyl ester of acrylic acid is ethyl acrylate.

3. A process of reducing the shrinking tendencies of wool-containing textile material which comprises impregnating-such a material with an inert, water dispersion containing a reactive. partly polymerized product of polymerization of a polymerizable composition and acatalyst for accelerating the curing thereof, said polymerizable composition including, by weight from about to 100% of a compound represented by the general formula l where It represents a hydrocarbon radical selected from the class consisting of alkyl, aralkyl, aryl and alkaryl radicals containing not more than 8 carbon atoms, and up to about 90% of a lower alkyl ester of acrylic acid, the take-up of the said dispersion being such as to deposit in the said textile material fromabout 2% to about 30%, based on the dry weight of the textile material, of the said polymerization product and containing, by weight, from to 85% of methoxyethyl acrylate and from 85 to 15% of a lower alkyl ester of acrylic acid, the amount of the said polymerization product with which the said textile material is impregnated being from about 2% to about by weight of the dry untreated textile, and heating the resulting treated material at a temperature within the range of from about 200 F. to about 300 F. to cure the said polymerization product, said cured product being substantially water-insoluble.

5. A process of treating woolen fabric material to reduce the shrinking tendencies thereof and to impart an improved finish thereto which comprises impregnating said fabric material with a composition comprising a reactive polymeric material and an organic peroxide as a catalyst for accelerating the curing thereof, said po ymeric material being a reactive, partly polymerized product of polymerization of a mixture containing, by weight, from 15 to of methoxyethyl acrylate and from 85 to 65% of ethyl acrylate, and the amount of the said reactive polymeric material with which the said fabric material is impregnated being from about 3% to about 15% by weight of the dry untreated fabric, and heating the resulting treated material at a temperature within the range of from about 200 F. to about 300 F. for a period sufficient to cure the said polymerization product substantially completely.

6. A process of treating woolen textile material to improve the properties thereof which comprises impregnating said textile material with a composition comprising a reactive, partly polymerized product of polymerization of a mixture containing, by weight, from 15 to 85% of ethoxyethyl acrylate and from 85 to 15% of a lower alkyl ester of acrylic acid, the amount of the said polymerization product with which the said textile material is impregnated being from about 2% to about 30% by Weight of the dry untreated textile, and heating the resulting treated material at a temperature within the range of from about 200 F. to about 300 F. to cure the said polymerization product, said cured product being substantially water-insoluble.

IIv

18 7. A process of treating woolen fabric mate rial to reduce the shrinkage tendencies thereof and to impart an improved finish thereto which comprises impregnating said fabric material with a composition comprising a reactive polymeric material and an organic peroxide as a catalyst for accelerating the curing thereof, said polymeric material being a reactive, partly polymerized product of polymerization of a mixture containing, by weight, from 15 to 35% of ethoxyethyl acrylate and from to 65% of ethyl acrylate the amount of the said reactive polymeric mate'lrial with which the said fabric material is impregnated being from about 3% to about 15% by weight of the dry untreated fabric, and heating the resulting treated material at a temperature within the range of from about 200 F. to about 300 F. for a period sufficient to cure the said polymerization product substantially completely.

8. A protein-containing textile material impregnated with a substantially water-soluble composition comprising a product of polymerization of a polymerizable composition including, by weight, from about 10% to 100% of a compound represented by the general formula where R represents a hydrocarbon radical se'- lected from the class consisting of alkyl, aralkyl, aryl and alkaryl radicals containing not more than 8 carbon atoms and up to about of a lower alkyl ester of acrylic acid, the amount of the said polymerization product with which the said textile material is impregnated being from about 2% to about 30% by weight of the dry untreated textile.

9. A protein-containing textile material impregnated with from about 2% to about 30%, by Weight of the dry untreated material, of a substantially water-insoluble composition comprising a product of polymerization of a polymerizable composition including, by weight from about 10% to of a compound represented by the eneral formula CH1=CH&-OCH2CH2OR where R represents an alkyl radical containing not more than 8 carbon atoms and up to about 90% of ethyl acrylate.

10. A woolen textile material which is resistant to shrinking and which is impregnated with from about 3% to about 15%, by Weight of the dry untreated material, of a substantially waterinsoluble polymer of methoxyethyl acrylate.

11. A woolen textile material which is resistant to shrinking and which is impregnated with from about 2% to about 30%, by weight of the dry untreated material, of a substantially waterinsoluble composition comprising a cured product of polymerization of a polymerizable mixture containing, by weight, from 15 to 85% of methoxyethyl acrylate and from 85 to 15% of a lower alkyl ester of acrylic acid.

12. A woolen textile material which is resistant to shrinking and which is impregnated with from about 2% to about 30%, by weight of the dry untreated material, of a substantially waterinsoluble composition comprising a cured product of polymerization of a polymerizable mixture containing, by weight, from 15 to 85% of ethoxyethyl acrylate and from 85 to 15% of a lower alkyl ester of acrylic acid.

13. A woolen fabric material which is resistant to shrinking and which is impregnated with 19 from about 3% to about by weight of the dry untreated material, of a cured, substantially water-insolubleproduct of polymerization-of a polymerizable mixture of, by weight, from 'l5to "of methoxyethyl acrylate and from 85 to of ethyl acrylate. 1

'14; A Woolen fabric material which is resistant to shrinking and which is impregnated with from about 3%"t0 about 15%, by weight of the dry untreated material, of a cured, substantially water-insoluble product of polymerization of a polymerizable mixture of, by weight, from 15 to 35% of ethoxyethyl acrylate and from to 65% of ethyl acrylate.

15. Shrink-resistant wool which is impregnated and coated with from about 3% to about 15%, by weight of the dry untreated wool, of a substantially water-insoluble composition comprising a cured product of polymerization of a polymerizable mixture of, by weight, about 75% methoxyethyl acrylate and about 25% ethyl acrylate.

16. A process of reducing the shrinking tendencies of protein-containing textile material which comprises treating said textile material with a reactive, partly polymerized product of polymerization of a polymerizable composition including, by weight, from about 10% to 100% of methoxyethyl acrylate and up to about of ethyl acrylate, the amount of the said polmerization product which is incorporated in the said 20 textile material'being from about 3% to about 15% by weight of the dry untreated textile, and heating the resulting treated material to cure the said polymerization product.

17. A process of reducing the shrinking tendencies of protein-containing textile material which comprises treating said textile material with a reactive, partly polymerized product of polymerization of a polymerizable composition including, by weight, from about 10% to ofethoxyethyl acrylate and up to about 90% of ethyl acrylate, the amount of the said polymerizationproduct which is incorporated in the said textile material being from about 3% to about 15% by weight of the dry untreated textile, and heating the resulting treated material to cure the said polymerization product.

ARTHUR S. N'YQUIST.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,099,047 Bradshaw Nov. 16, 1937 7 2,843,093 Smith Feb. 29, 1944 2,406,412 Speakman et al Aug. 27, 1946 McQueen Sept. 3. 1946 Certificate of Correction Patent No. 2,565,259 August 21, 1951 ARTHUR S. NYQUIST It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 6, line 23, for devided read divided; column 14, line 73, for toulene read toluene; column 15, link: i, for other read others; column 18, line 2, for shrinkage read shrinking;

and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 22nd day of January, A. D. 1952.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

1. A PROCESS OF TREATING PROTEIN-CONTAINING TEXTILE MATERIAL TO IMPROVE THE PROPERTIES THEREOF WHICH COMPRISES TREATING SAID TEXTILE MATERIAL WITH A REACTIVE, PARTLY POLYMERIZED PRODUCT OF POLYMERIZATION OF A POLYMERIZABLE COMPOSITION INCLUDING, BY WEIGHT, FROM ABOUT 10% TO 100% OF A COMPOUND REPRESENTED BY THE GENERAL FORMULA 